3,4-dichloro-1-(alpha-chloro-beta-trichloroethyl)-benzene



Patented Aug. 2, 1949 :UmrE-o i SiTAT-ES PATENT IQFFICE v3,4-DIonLoRo-1- (a-CHLORO-fl-TRI- ,CHLOROETHYL) -BENZENE CharlesGraenacher, Riehen, and Paul Streuli,

'Max Geiger, and Eduard Usteri, Basel, Switzerland, assignors to .Cib'aLimited;- BaseL 'switzerland, a Swiss firm N Drawing. Application lflayl l, 1947, Serial No. 748,122. In Switzerland May 17,1346

1 Claim. (01:260-651) According 2 to i this invention 3:4-di-chloro-1-wtetrachlorethyl-benzene of the formula .is Jnade .-,by condensingortho-dichlorobenzene i ....with .chloral ,or condensing3.:4-dichlorobenzaldehydewith.chloroform,and exchanging the hydroxylgroup .111 the resulting carbinol fora chlomrine atom.

The. product, which may. morespeciflcally be .termed 3 :4 dichloro-l-(a-chloro-p-trichlorvethylhbenzene, .is a water-clearoil having a feeblyaromatic odour and boiling at 1'72-1!75., C. under,11.mm.,pressure.

The condensation .of .ortho-diohlorobenzene with chloral is conducted inthe presenoeof a .condensing agent, advantageously anhydrous Theproduct; of theinvention .is a remarkably suitable agent for combatinganimal pests. It

acts onthe various stagesinthe-developmentof the pests, for example, asa contact, stomach or respiratory poison.

It can be used for protecting a very widevarietyof things against pests,and gaseous ,or liquid or solid substances may 'be .used as ,carriersfor the active substance.

As things to be protected or to'rbe used as carriers there come intoconsideration for example, the; air, especially in rooms, andliquids,Ifor. instance .water. in.,ponds,

and .finally any. living. or,..non-living'solidsubstratum; for instance,the objects in living-rooms,

,in;cel1 ars,.on;plaster floorsorin stables,.alsopelts, "feathers, wooland the like as .well asliving organisms of the vegetable and animalkingdoms in their very wide variety of states of development, providedthat they are not sensitive to the pest-combating agent.

The pests are oombated by the usual methods bytreating the thing to beprotected with .3 1- chloro 1 (a-chloro-fi-trichlorethyl) benzene in'theform of vapour or of a spraying or dusting preparation. Solutionsorsuspensions in'water or'ln suitable organic solvents,-forexample,.al.co- ,hol, petroleum, tar distillates and others, or.aqueous. solutions. vorraq eous ,...emu1sions,. of organic solventsmay. .be used forbrushing, spraying. or dippingthepbjects t beprotected. They may also be dusted withoutvicausing materially ,in-

jurious effectson warm blooded animals. In order to enhance the "wettingand adhering capacity there may: be added the usual wetting agents,"for; example; butyl-naphthalene sulfonic 15.-.acid;- fatty-alcohol;sulfonatesand the like, and

:1 adhering; agents, fox-example, hardenable aminoplasts; amongrzwhich;,hardenable carbamide or melamine resins=-.sol ub1e,,in (waterorof-restricted :water-solubilityl.are.included. If desired, there may Ialso 5136 .added' ;-inert :-:zfil 1ing materials .or

..identi,fying ematerials, ;,for example, kaolin, .zqgypsum :orbentonite or othergadditions' such; as

. :isulfitexcelluloseg waste liquor, cellulose derivatives The:3:4edichloro,-1:- (a-i chloro-p-trichlorethyl) izabenzene mayalso.beiusedin admixture with other vpest-combating agents.

i Theginsecticidalactivity of' 3-:4 -dichloro-1 a-:chloro-flgtrichlorethfl) -.ben zene will be clearly understood fromJiihdqfOllOWiHg data I. Paotoncm Connor The test animals were broughtinto-contact with. an1 accurately {dosed coating in. Petri dishes oflmcentimeters diameter, and continuously 30b- EISBI'VBd. '1 'J Thecoating was prepared by placing; an ethereal: solutiongtof, the activesubstance in the :dish-yand-.allowing-the-solventto. evaporate.

40; (a) Results with 0.1. milligram: of, the active substance; per Isquare centimeter i5. 1 3 o ,-.24- ....48 'minswhourhours hours hourshours -';;Musca domestica 1 Calliphora, ,ervtrocephv ala n63 Tinea'granellann n'n --(B Gncthocemsoomutus" 1, 63". Phyllodromia germam'ca a)Lasius fulz'ginosus (B Liposcelis divlnatorms" a) carbonate and thenwith water.

(b) Tests on flies with weak coatings Test animals: Musca domestica II.BRIEF CONTACT Test animals: Musca domestica 7 r V 0.1 milligram of theactive substance per square centimeter. I i The animals were subjected.for a limited period to the action of the coating, and subsequentlyobserved in clean dishes.

Period of contact 1 hour 24 hours 30 minutes G9 15 minutes. 69 minutes.63 2 minutes. 63 1 minute 63 In the foregoing tablesd: $=anirnalsparalysed and lying on their backs, +=enimals kllle i V The followingexamples illustrate the invention, the parts being by weight unlessotherwise stated, and the relationship of parts by weight to parts byvolume being the same as that of the kilogram to theliter:

EXAMPLE 1 240 parts of anhydrous aluminium chloride are introduced insmall portions with the exclusion of moisture in the course of 5 hoursinto a soludried. The excess of dichlorobenzene is then removed bydistillation under reduced pressure, and the dark oil which remainsbehind is then fractionated under greatly reduced pressure. 3 4 dichloro1 (u-hydroxy-fi-trichlorethyl) benzene is obtained in good yield in theform of a viscous oil boiling at 153-154" C. under 0.06 mm.

pressure. 7 I

450 parts of the carbinol so obtained are dissolved in 1000 parts byvolume of ether, and then 340 parts of phosphorus pentachloride areslowly introduced, while stirring, and with the exclusion of moisture. Ihe reaction temperature is maintained at 0-15" C. by means of an icebath. When the whole of the phosphorus pentachloride has been introducedand the evolution of hydrogen chloride has ceased, first the ether andthen the phosphorus oxychloride formed are removed by distillation. Theresidual oil is well washed first with a dilute aqueous solution ofsodium After being dried, the oil is fractionated over 10 parts of solidsodium carbonate under reduced pressure. A good yield of 3:4-dichloro-l-(a-ohloro-fl-trichlor- 4 ethyl) -benzene is obtained inthe form of an oil with a feebly aromatic odour and having a boilingpoint of 172-175 C. under 11 mm. pressure.

EXAMPLE 2 20 parts of finely powdered dry potassium hy- 'droxide areintroduced 'in small portions into a solution of 174 parts of3:4-dichlorobenzaldehyde in 120 parts of dry ether and parts of drychloroform in the course of 4 hours, while stirring, and with theexclusion of moisture. The reaction temperature is maintained at 15-20C. by external cooling. When the whole of the potassium hydroxide hasbeen introduced, the mixture is stirred for a further 12 hours at 20 C.and then allowed to stand for 48 hours. The reaction mixture is thenmixed with ice-water, and the ethereal layer is separated, washedneutral with water, dried, and the ether is removed by distillation. Theoil which remains behind is fractionated under greatly reduced pressure.A good yield of 3 :4-dichloro-1- (a-hydroxy-fl-trichlorethyl) -benzeneis obtained in the form of a clear oil boiling at 153-154" C. under 0.06mm. pressure.

450 parts of the carbinol so obtained are dissolved in 1000 parts byvolume of ether, and then 325 parts of phosphorus pentachloride areslowly introduced while stirring and with the exclusion of moisture.Thereaction temperature is maintained at 0-15 C. by cooling in an icebath. When the whole of the phosphorus pentachloride has been introducedand the evolution of hydrogen chloride has ceased, first the ether andthen the phosphorus oxychloride formed are removed by distillation. Theresidual oil is well washed first with a dilute aqueous solution ofsodium carbonate and then with water, dried, and fractionated underreduced pressure. A good yield of 3 :4- dichloro-1-(a-chloro-[i-trichloroethyl) benzene is obtained in the form of awater-clear oil boiling at 172-175 C. under 11 mm. pressure.

What we claim is:

314-dichloro-1-tetrachlorethyl-benzene of the formula The followingreferences are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,010,841 Bender Aug. 13, 19352,329,074 Muller Sept. 7, 1943 OTHER REFERENCES Chattaway et al.,"Journal of the Chemical Society, (London) 1934, pages 701-2.

Haller et al., Jour. Am. Chem. $00., vol. 67, page 1593 (1945).

Haller et al., J. A. Chemical Society, Sept. 1945, pages 1591-1593.

